The present invention relates to a stabilized organic polymer material composition wherein the organic polymer material susceptible to degradation due to oxidation, heat or light has become hardly degraded in qualities, such as physical properties, appearance and the like, even after thermal hysteresis during processing and in use. The present invention also relates to a stabilizer composition for organic polymer material, which is an additive used for obtaining a stabilized organic polymer material composition.
An organic polymer material comprising organic compounds, such as natural polymer, synthetic polymer, fats and oils, lubricant oil, working oil and the like, is susceptible to degradation by oxidation, heat, light and the like, and loses utility. Therefore, various stabilizers called antioxidants are added to organic polymer materials to give organic polymer material compositions that are not easily degraded.
A compound of the formula 
wherein R1 is alkyl having 1 to 18 carbon atoms or alkenyl having 2 to 18 carbon atoms, R2 is alkyl having 1 to 5 carbon atoms, R3, R4 and R5 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms, and R6 is hydrogen atom or alkyl having 1 to 5 carbon atoms, is widely known as an antioxidant for fats and oils and polyolefin.
For example, compounds of the formula (1), wherein R1 and R2 are both methyl, are disclosed in JP-B-42-11064, U.S. Pat. No. 3,476,772, Chemical Abstracts, vol. 70, 2500, ibid., vol. 50, 15104 and ibid., vol. 72, 13900, German Patent No. 114916 and JP-A-49-72338, as antioxidants. However, since marked coloring of organic polymer materials containing these 6-hydroxychroman compounds has not been overcome, these 6-hydroxychroman compounds have not been widely used as antioxidants.
Meanwhile, vitamin E (tocopherol), wherein R1 is alkyl having 16 carbon atoms and R2 is methyl, is a natural substance and is widely used for the prevention of oxidation of foodstuffs.
In 1940s, a phosphorus compound was studied as an antioxidant and some phosphorus antioxidants have since been used in an extremely broad range.
For example, JP-A-1-254744 discloses tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite.
JP-A-5-178870 discloses tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite and a composition containing this compound.
JP-A-8-231568 discloses (2,4-di-tert-butylphenoxy)bis[4xe2x80x2-[bis(2,4-di-tert-butylphenoxy)phosphino]biphenyl-4-yl]phosphine, (2,4-di-tert-butyl-5-methylphenoxy)bis[4xe2x80x2-[bis(2,4-di-tert-butyl-5-methylphenoxy)phosphino]biphenyl-4-yl]phosphine and the like and the compositions containing these compounds.
JP-A-9-238490 discloses 2,4-di-tert-butylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl]phosphinite, 2,4-di-tert-butyl-5-methylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl]phosphinite and the like and the compositions containing these compounds.
The above-mentioned publications teach that these compounds and the compositions containing these compounds are effective stabilizers for organic polymer materials.
Besides these, aryl phosphite compounds such as tris(2,4-di-tert-butylphenyl)phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and the like have been used as antioxidants.
In addition, pentaerythritol phosphite compounds such as bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(2,4-di(1-phenyl-1,1-dimethylmethyl)phenyl) pentaerythritol diphosphite, (2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediol phosphite, bisisodecyloxy pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite and the like have been used as antioxidants.
Moreover, bisarylalkyl phosphite (oxaphosphocin) compounds such as 2,2-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite] and the like have been used as phosphorus antioxidants.
In 1930s, a phenolic compound was studied as an antioxidant and some phenolic antioxidants have since been used in an extremely broad range.
For example, generally used phenolic antioxidants are exemplified by n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like.
In addition, plural kinds of antioxidants have been widely used in combination to allow simultaneous expression of different effects or synergistic effect.
For example, JP-A-53-78248 teaches a method for preventing yellowing by the use of a polyolefin composition containing a 6-hydroxychroman compound and a phenolic antioxidant, such as 2,6-di-tert-butyl-4-methylphenol and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane. In this specification, 0.005-0.5 part by weight, preferably 0.01-0.2 part by weight, of a 6-hydroxychroman compound, and 0.005-1 part by weight, preferably 0.01-0.5 part by weight, of a phenolic antioxidant are added to 100 parts by weight of a resin.
JP-A-54-20056 discloses a thermoplastic polymer having an improved heat stability, which contains a 6-hydroxychroman compound. It is taught that a 6-hydroxychroman compound is added in a proportion of 0.005-0.2 part by weight, preferably 0.01-0.1 part by weight, per 100 parts by weight of a resin. When the content is less than 0.005 part by weight, the heat stabilizing effect is taught to be little.
JP-A-53-114852 teaches that a polyolefin having superior stability can be obtained by adding a 6-hydroxychroman compound and a phenolic antioxidant (e.g., 2,6-di-tert-butyl-4-methylphenol, 2,2-methylenebis(4-ethyl-6-tert-butyl)phenol and the like). This publication teaches the addition of 0.005-0.5 part by weight, preferably 0.01-0.2 part by weight, of a 6-hydroxychroman compound and 0.01-5 parts by weight, preferably 0.05-1.0 part by weight, of a phenolic antioxidant to 100 parts by weight of a resin.
Since a phenolic antioxidant and a phosphorus antioxidant show different actions, a combined use of these has been proposed. A phosphorus compound is used as a secondary antioxidant and a hindered phenol compound is used as a primary antioxidant during the processing of a synthetic resin, thereby to improve coloring of an organic polymer material.
For example, JP-B-4-69657 discloses a polyolefin composition containing a 6-hydroxychroman compound and tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphite, both in a proportion of 0.01-1 wt%.
JP-A-63-137941 discloses a composition containing vitamin E (0.005-0.5 part by weight, preferably 0.03-0.3 part by weight) and tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphite (0.005-0.5 part by weight, preferably 0.03-0.3 part by weight) per 100 parts by weight of a resin, as a polyolefin composition superior in heat stability and hue. It also teaches that a vitamin E content of less than 0.005 part by weight per 100 parts by weight of a resin results in improved hue but insufficient heat stabilizing effect during forming processing.
JP-A-62-86036 teaches that addition of a 6-hydroxychroman compound (0.005-0.5 part by weight, preferably 0.01-0.2 part by weight) and a phosphorus antioxidant of distearyl pentaerythritol phosphite or tris(2,4-di-tert-butylphenyl) phosphite (0.01-0.5 part by weight, preferably 0.02-0.3 part by weight) to 100 parts by weight of a resin results in improved stability of polyolefin, improved coloring property and a black spot problem. It also teaches that a phenolic antioxidant can be added.
JP-A-2-225542 teaches a polyolefin composition stabilized by the addition of a 6-hydroxychroman compound (0.01-1 part by weight, preferably 0.05-0.5 part by weight) and a phosphorus antioxidant of a specific phosphite compound (0.01-1 part by weight) to 100 parts by weight of a resin. It also teaches that, when a 6-hydroxychroman compound is added in a proportion of less than 0.01 part by weight relative to 100 parts by weight of a resin, the stability during processing cannot be improved sufficiently.
The technique disclosed in these publications aims at solving the problem of coloring of a resin, ignoring the superiority of a 6-hydroxychroman compound inclusive of vitamin E as an antioxidant or stabilizer during processing, and adds the smallest possible amount (0.005 part by weight or above per 100 parts by weight of a resin) of a 6-hydroxychroman compound inclusive of vitamin E along with other antioxidant.
The content of a 6-hydroxychroman compound inclusive of vitamin E is, as in the phenolic antioxidants conventionally used, taught to be 0.005 part by weight-0.5 part by weight relative to 100 parts by weight of an organic polymer, but the mixing ratio of a 6-hydroxychroman compound and a phosphorus antioxidant is not referred to or suggested.
That is, JP-A-53-78248 teaches a method for preventing yellowing but is silent on stability during processing. A phosphorus antioxidant is not contained, and the proportion of the 6-hydroxychroman compound relative to the total amount of the antioxidants in the case of Examples is calculated to be 22.2%-15.7%. In addition, JP-A-54-20056 teaches the synergistic effect provided by the concurrent use of a 6-hydroxychroman compound and a phenolic antioxidant, but the amount of the phenolic antioxidant is 0.01-1 part by weight relative to 100 parts by weight of a resin, and no further disclosure is found even in Examples. In an Example, a 6-hydroxychroman compound alone is added to a resin.
JP-A-53-114852 discloses concurrent use of a 6-hydroxychroman compound and plural phenolic antioxidants, but in an Example, vitamin E was added in a proportion of 0.03 part by weight and two kinds of phenolic antioxidants were added respectively in a proportion of 0.1 part by weight relative to a resin, wherein the proportion of the 6-hydroxychroman compound to the total amount was about 13 wt %.
JP-A-63-137941 discloses, in Examples, the addition of vitamin E in a proportion of 0.03 part by weight or 0.10 part by weight, and tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite in a proportion of 0.03 part by weight, relative to 100 parts by weight of a resin, wherein the proportions of the 6-hydroxychroman compound to the total amount of the antioxidants are 50% and 77%.
JP-A-62-86036 discloses an example wherein vitamin E is added in a proportion of 0.05 part by weight, and distearyl pentaerythritol phosphite or tris(2,4-di-tert-butylphenyl)phosphite is added in a proportion of 0.05 part by weight, 0.2 part by weight and the like, relative to 100 parts by weight of a resin, and the proportions of the 6-hydroxychroman compound to the total amount of the antioxidants are 50% and 20%.
JP-A-2-222542 discloses an example wherein vitamin E is added in a proportion of 0.05 part by weight, and a specific phosphite compound (phosphorus antioxidant) is added in a proportion of 0.05 part by weight, relative to 100 parts by weight of a resin. The ratio of these is 1:1, wherein the proportion of the 6-hydroxychroman compound to the total amount of the antioxidants is 50%.
The above-mentioned publications disclose the concurrent use of two kinds of components of a 6-hydroxychroman compound and a phenolic antioxidant, or a 6-hydroxychroman compound and a phosphorus antioxidant, but three kinds of components of a 6-hydroxychroman compound, a phenolic antioxidant and a phosphorus antioxidant is only referred to without specific disclosure, not to mention any disclosure or suggestion of a mixing ratio of a 6-hydroxychroman compound and a phenolic or phosphorus antioxidant. Therefore, the above-mentioned publications do not disclose or suggest, unlike the present invention, that a phenolic antioxidant, a phosphorus antioxidant, and a small amount of a 6-hydroxychroman compound are added to an organic polymer material, thereby to inhibit coloring and to provide a remarkable synergistic effect on stability during processing.
For example, JP-A-63-105060 or U.S. Pat. No. 4,806,580 teaches that a stabilizer composition for a synthetic resin, which contains 1 part by weight of vitamin E and 5-14 parts by weight of a specific phosphorus antioxidant, such as tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphite and the like, shows improved stability with regard to coloring. It discloses, in a comparative example, a composition containing 1 part by weight of vitamin E and 15 or 16 parts by weight of a specific phosphorus antioxidant such as tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphite and the like.
JP-A-63-105060 teaches, at page 2, lower left column referring to the background of the invention, that a more preferable compound from the aspects of hygiene and safety is desired, and as a phenolic antioxidant, naturally occurring vitamin E and a 6-hydroxychroman compound having a similar structure to vitamin E can be used as substitutes for the previously used phenolic antioxidants.
The mixing ratio disclosed in this publication can be calculated into about 6.7 wt %-about 16.7 wt % of vitamin E of the total amount of vitamin E and the phosphorus antioxidant, and the compositions of comparative examples wherein the ratios are about 6.3 wt % and about 5.9 wt % are disclosed to show poor stabilizing effect.
This publication proposes an organic polymer material composition containing a 6-hydroxychroman compound and a phosphorus antioxidant, instead of a phenolic antioxidant and a phosphorus antioxidant previously used. This is a proposition of a mixture taking a 6-hydroxychroman compound under the category of phenolic compounds, and the mixing ratio of the antioxidants is different from that in the present invention.
That is, these prior art techniques are different from the resent invention which, by the use of a stabilizer composition containing a phenolic antioxidant, a phosphorus antioxidant having synergistic effect and an extremely small amount of a 6-hydroxychroman compound of the formula (1), aims at strikingly enhanced stability during processing while maintaining the heat resistance provided by the phenolic antioxidant and the coloring preventive effect provided by the phosphorus antioxidant. In the present invention, a 6-hydroxychroman compound can be considered an agent for reinforcing the stability during processing of a phenolic antioxidant and a phosphorus antioxidant.
In recent years, 3-arylbenzofuranone compound has been developed as a synergist of a phosphorus antioxidant and a phenolic antioxidant. In the meantime, JP-A-7-233160 in Example 14 shown at the paragraph No. 0226 discloses 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-3H-benzofuran-2-one (compound 103 in this application) that can be used for the object similar to the object of the present invention. This compound is also described in the material for the lecture by C. Krohnke entitled xe2x80x9cA major breakthrough in polymer stabilizationxe2x80x9d reported in the international convention relating to polyolefin (Polyolefins X international conference) held in Houston, Tex. on Feb. 23-26, 1997, as a synergist for phenolic antioxidants and phosphorus antioxidants. However, the synergistic effect is not satisfactory, and a more effective synergist has been demanded.
A recent growing demand on an antioxidant effective for achieving superior heat stability and superior stability during processing, that permit higher temperature for high speed molding and high temperature molding of an alloy with an engineering plastic and the like, cannot be fully met by these known stabilizing compositions. Moreover, an antioxidant effective by the addition of a small amount thereof to achieve heat resistance and stability during processing has been increasingly demanded.
As a means to improve a stabilizing effect of an organic polymer material, WO97/49758 discloses a stabilizer composition containing a phenolic antioxidant, a phosphorus antioxidant and vitamin E (tocopherol), wherein the weight ratio of phenolic antioxidant:phosphorus antioxidant is 2:1-1:4, and the weight ratio of phenolic antioxidant:vitamin E is 2:1-10:1. This publication discloses that this stabilizer composition is highly effective for the prevention of decomposition, crosslinking and coloring of a polymer material due to heat or light. This publication also teaches that the weight ratio of phenolic antioxidant:phosphorus antioxidant is preferably 1:1 and the weight ratio of phenolic antioxidant:vitamin E is preferably 5:1.
Vitamin E is susceptible to oxidation by air, shows marked coloring and is a viscous liquid. It is defective in that the handling of vitamin E requires special facility and the like. In addition, vitamin E may be used in a small amount as an antioxidant of food in view of safety, but rarely applied to an industrial use such as a stabilizer for an organic polymer material to be added to a resin.
Since vitamin E is a viscous liquid, homogeneous dispersion of vitamin E in a composition to give the composition defined in the claims of WO97/49758 is difficult in an industrial large scale production. Particularly, homogeneous dispersion of vitamin E in a composition is very difficult, thus resulting in inconsistent property of the obtained compositions.
According to the study of the present inventors, a composition containing the phenol antioxidant, the phosphorus antioxidant and a small amount of vitamin E is powdery when mixed, but since the powder has moisture, it grows sticky in the course of long-term preservation and becomes extremely difficult to handle.
According to the study of the present inventors, moreover, the addition of vitamin E to the phenolic antioxidant and the phosphorus antioxidant has been found to cause blocking (agglomeration of powder) during long-term storage.
According to the study of the present inventors, a composition containing a phenolic antioxidant, a phosphorus antioxidant and a small amount of vitamin E showed a decreased content of the phosphorus antioxidant during a long term storage. When such a composition after a long term storage was added to an organic polymer material such as a synthetic resin, an improving effect of stability during processing of the organic polymer material and a coloring preventive effect were found to be degraded.
It has been found by the study of the present inventors that a composition containing a phenolic antioxidant, a phosphorus antioxidant and a small amount of vitamin E is associated with a problem of low stability during a long term storage.
It is an object of the present invention to provide a superior antioxidant (stabilizer for organic polymer material) effective for preserving stability during processing and heat resistance with a small amount thereof, while maintaining coloring preventive effect.
It is also an object of the present invention to provide an antioxidant (stabilizer for organic polymer material), which is stable during long-term storage.
The present inventors have conducted studies in an attempt to solve the above-mentioned problems and found that a stabilizer superior in improving a coloring preventive effect, heat resistance and stability during processing of an organic polymer material can be obtained by mixing a small amount of a 6-hydroxychroman compound of the following formula (1) with a stabilizer composition containing a phosphorus antioxidant and a phenolic antioxidant. The present inventors have further found that the stabilizer composition of the present invention prevents stickiness and blocking during a long term storage, and also suppresses reduction of an antioxidant component content, reduced improvement of stability during processing, and reduced coloring preventive effect. Thus, the stabilizer composition of the present invention is superior in stability of the stabilizer composition itself during long term storage, as compared to a stabilizer composition containing a phosphorus antioxidant, a phenolic antioxidant and vitamin E.
The present invention solves the above-mentioned problems and provides the following.
A stabilizer composition for an organic polymer material, which comprises (a) at least one member from the compounds of the formula (1) 
wherein R1 is alkyl having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms, R2 is alkyl having 1 to 5 carbon atoms, R3, R4 and R5 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms, and R6 is hydrogen atom or alkyl having 1 to 5 carbon atoms (hereinafter also to be referred to as 6-hydroxychroman compound);
(b) a phosphorus antioxidant; and
(c) a phenolic antioxidant,
wherein the component (a) is contained in a proportion of 0.5 wt %-10 wt % and the total of the component (b) and the component (c) is in a proportion of 99.5 wt %-90 wt %, of the total amount of the component (a), the component (b) and the component (c).
The present invention provides the above-mentioned stabilizer composition, wherein the component (a) is contained in a proportion of 1.0 wt %-6.5 wt %, and the total amount of the component (b) and the component (c) is in a proportion of 99.0 wt %-93.5 wt %, of the total amount of the component (a), the component (b) and the component (c). The present invention also provides the above-mentioned stabilizer composition, wherein the component (a) is contained in a proportion of 1.0 wt %-4.5 wt %, and the total amount of the component (b) and the component (c) is in a proportion of 99.0 wt %-95.5 wt %, of the total amount of the component (a), the component (b) and the component (c).
The present invention provides the above-mentioned stabilizer composition, wherein the weight ratio of the component (b):component (c) is 9:1-1:9.
The stabilizer composition of the present invention may further contain a sulfuric antioxidant and/or a light stabilizer.
The present invention provides an organic polymer material composition comprising an organic polymer and the above-mentioned stabilizer composition. The organic polymer material composition of the present invention may further contain a sulfuric antioxidant and/or a light stabilizer.
The present invention also provides an organic polymer material composition comprising
(a): at least one member from the compounds of the formula (1) 
wherein R1 is alkyl having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms, R2 is alkyl having 1 to 5 carbon atoms, R3, R4 and R5 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms, and R6 is hydrogen atom or alkyl having 1 to 5 carbon atoms;
(b): a phosphorus antioxidant;
(c): a phenolic antioxidant; and
(d): an organic polymer,
wherein the component (a) is contained in a proportion of 0.0005 part by weight-0.025 part by weight per 100 parts by weight of the organic polymer material composition.
The present invention provides the above-mentioned organic polymer material composition wherein the component (a) is contained in a proportion of 0.0005 part by weight-0.010 part by weight per 100 parts by weight of the organic polymer material composition.
The present invention provides the above-mentioned organic polymer material composition, wherein the weight ratio of component (b):component (c) is 9:1-1:9.
The organic polymer material composition of the present invention may further contain a sulfuric antioxidant and/or a light stabilizer.
In the present invention, a phosphorus antioxidant (the component (b)) can be a phosphorus antioxidant selected from the following (b-1), (b-2), (b-3) and (b-4). (b-1): A compound of the formula (2) 
wherein Q1 is a group of the formula (3) 
wherein R7 and R8 are the same or different and each is alkyl having 1 to 4 carbon atoms, and R9 is hydrogen atom or methyl, Q2 is, independently from other repeating units, a group of the formula (3) 
wherein each symbol is as defined above, i is, independently from other repeating units, 0 or 1, j is 0 or 1, and n1 is an integer of 1 to 10, or of the formula (4) 
wherein each symbol is as defined above.
(b-2): A compound of the formula (5) 
wherein each R10 is the same or different and is alkyl having 1 to 18 carbon atoms, phenyl, phenyl substituted by alkyl having 1 to 9 carbon atoms, or a group of the formula (6) 
wherein R12 and R13 are the same or different and each is alkyl having 1 to 4 carbon atoms, and R14 is hydrogen atom or methyl, and R11 is alkyl having 1 to 18 carbon atoms, phenylalkyl having 7 to 9 carbon atoms, cyclohexyl, phenyl, phenyl substituted by alkyl having 1 to 9 carbon atoms, or a group of the formula (6) 
wherein R12 and R13 are the same or different and each is alkyl having 1 to 4 carbon atoms, and R14 is hydrogen atom or methyl, or of the formula (7) 
wherein R10 is as defined above, n4 is 3, and L1 is 1,1,3-butanetriyl.
(b-3): A compound of the formula (8) 
or of the formula (9) 
wherein q is 1 or 2, wherein, when q is 1, A is a group of the formula (10) 
wherein R18 and R19 are the same or different and each is alkyl having 1 to 4 carbon atoms, and R20 is hydrogen atom or alkyl having 1 to 4 carbon atoms, and when q is 2, A is alkylene having 2 to 18 carbon atoms, p-phenylene or p-biphenylene, R15 and R16 are each independently alkyl having 1 to 4 carbon atoms, and each R17 is independently alkyl having 1 to 18 carbon atoms, phenylalkyl having 7 to 9 carbon atoms, cyclohexyl, phenyl, or a group of the formula (11) 
wherein R21 and R22 are the same or different and each is alkyl having 1 to 4 carbon atoms or phenylalkyl having 7 to 9 carbon atoms, and R23 is hydrogen atom or alkyl having 1 to 4 carbon atoms. (b-4): A compound of the formula (12) 
wherein each R24 is the same or different and is alkyl having 1 to 5 carbon atoms, each R25 is the same or different and is hydrogen atom or alkyl having 1 to 5 carbon atoms, each R26 is the same or different and is hydrogen atom or methyl, R27 is direct bond, methylene, xe2x80x94CH(R29)xe2x80x94(R29 is alkyl having 1 to 4 carbon atoms) or sulfur atom, and n3 is 1 or 3, wherein when n3 is 3, R28 is a group of the formula N(CH2CH2O)3, and when n3 is 1, R28 is alkyl having 1 to 18 carbon atoms, halogen atom, hydroxy or alkoxy having 1 to 8 carbon atoms.
In the present invention, the following phosphorus antioxidant (b-5) can be used as the phosphorus antioxidant (component (b)).
(b-5): At least one member from the compounds of the formula (17) 
xe2x80x83wherein
R33 and R34 are the same or different and each is hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms, aralkyl having 7 to 12 carbon atoms or phenyl; each R35 is the same or different and is hydrogen atom or alkyl having 1 to 8 carbon atoms;
R36 is a direct bond, methylene, xe2x80x94CH(R42)xe2x80x94 wherein R42 is alkyl having 1 to 7 carbon atoms or cycloalkyl having 5 to 8 carbon atoms, or sulfur atom;
R37 is alkylene having 2 to 8 carbon atoms, *-R43xe2x80x94O-CO-R44xe2x80x94or *xe2x80x94COxe2x80x94R44xe2x80x94wherein R43 is alkylene having 1 to 8 carbon atoms, R44 is a direct bond or alkylene having 1 to 8 carbon atoms and * means bond on the oxygen atom side; R38 and R40 are the same or different and each is hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms, aralkyl having 7 to 12 carbon atoms or phenyl; and one of R39 and R41 is hydroxyl group, alkoxy having 1 to 8 carbon atoms or aralkyloxy having 7 to 12 carbon atoms and the other is hydrogen atom or alkyl having 1 to 8 carbon atoms.
A preferred phosphorus antioxidant (b-1) is a compound of the formula (13) 
wherein Q3 is a group of the formula (14) 
wherein R9 is hydrogen atom or methyl, Q4 is, independently from other repeating units, a group of the formula (14) 
wherein R9 is hydrogen atom or methyl, i is, independently from other repeating units, 0 or 1, j is 0 or 1, and n2 is an integer of 1 to 3, or of the formula (15) 
wherein each symbol is as defined above.
Preferable phosphorus antioxidant (b-1) is, for example, at least one member selected from the group consisting of
tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite,
tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite,
(2,4-di-tert-butylphenoxy)bis{4xe2x80x2-(bis(2,4-di-tert-butylphenoxy)phosphino)biphenyl-4-yl}phosphine, and
(2,4-di-tert-butyl-5-methylphenoxy)bis{4-(bis(2,4-di-tert-butyl-5-methylphenoxy)phosphino)biphenyl-4-yl}phosphine.
Preferable phosphorus antioxidant (b-2) is, for example, at least one member selected from the group consisting of
tris(2,4-di-tert-butylphenyl) phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,
triphenyl phosphite,
diphenyl alkyl phosphite,
phenyl dialkyl phosphite,
tris(nonylphenyl) phosphite,
trilauryl phosphite,
trioctadecyl phosphite and
bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite.
Preferable phosphorus antioxidant (b-3) is, for example, at least one member selected from the group consisting of
bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,
bis(2,4-di(1-phenyl-1,1-dimethylmethyl)phenyl) pentaerythritol diphosphite,
(2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediol phosphite,
bisisodecyl pentaerythritol diphosphite and
bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite.
Preferable phosphorus antioxidant (b-4) is, for example, at least one member selected from the group consisting of
2,2-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin and
2,2xe2x80x2, 2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2, 5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite].
Preferable phosphorus antioxidant (b-5) is, for example, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin.
In the present invention, a phenolic antioxidant (component (c)) can be a compound having one or more structures shown by the following Formula (16) 
wherein R30 is alkyl having 1 to 5 carbon atoms, R31 is alkyl having 1 to 4 carbon atoms, R32 is hydrogen atom or methyl, and L is 
in a molecule.
Preferable phenolic antioxidant is, for example, at least one member selected from the group consisting of
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane,
n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like.
More preferably, at least one member selected from the group consisting of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane and n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
The organic polymer in the organic polymer material composition of the present invention can be a synthetic resin. Preferably, this organic polymer is a polyolefin resin. More preferably, it is a polyethylene resin, a polypropylene resin, a mixture or a compatible polymer of a polyethylene resin and a polypropylene resin, a compatible polymer containing a polyethylene resin and/or a polypropylene resin, an ethylene-vinyl acetate copolymer or an ethylene-propylene copolymer.
According to the present invention, an organic polymer material composition comprising a synthetic resin and the stabilizer composition of the present invention wherein the weight ratio of component (b):component (c) is 9:1-1:9 can be provided. This synthetic resin is preferably a polyolefin resin. The component (c) is preferably at least one member selected from the group consisting of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane and n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The component (b) is preferably at least one member selected from the group consisting of tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite and tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite.
According to the present invention, an organic polymer material composition comprising a synthetic resin and the stabilizer composition of the present invention, wherein the component (a) is 2,2,5,7,8-pentamethyl-6-hydroxychroman and the weight ratio of component (b):component (c) is 9:1-1:9, is provided. This synthetic resin is preferably a polyolefin resin. The component (c) is preferably at least one member selected from the group consisting of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane and n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The component (b) is preferably at least one member selected from the group consisting of tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite and tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite.
The present invention also relates to a stabilizer composition or organic polymer material, which comprises
a): at least one member from the compounds of the formula 
wherein R1 is alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms, R2 is methyl, and R3, R4, R5and R6 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms;
(b): a phosphorus antioxidant; and
(c): a phenolic antioxidant,
wherein the component (a) is contained in a proportion of 1 wt %-20 wt % and the component (c) is contained in a proportion of 99 wt %-80 wt %, relative to the total amount of the component (a) and the component (c).
The substituents of the compound of the formula (1), 
which is the constituent component of the stabilizer composition for organic polymer material of the present invention, are explained in the following.
R1of compound of the formula (1) is alkyl having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms, and the alkyl and alkenyl may be a straight or branched chain. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl and the like.
A preferable group at R1 of the compound of the formula (1) is methyl.
R2of the compound of the formula (1) is linear or branched alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl and the like.
A preferable group at R2 of the compound of the formula (1) is methyl.
R3, R4 and R5 of the compound of the formula (1) are the same or different and each is hydrogen atom or linear or branched alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like.
Preferable examples of R3, R4 and R5 of the compound of the formula (1) include hydrogen atom, methyl, isopropyl and tert-butyl, more preferably hydrogen atom and methyl, particularly preferably methyl.
R6 of the compound of the formula (1) is hydrogen atom or linear or branched alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl and the like.
A preferable group at R6 of the compound of the formula (1) is hydrogen atom.
The compound of the formula (1) is exemplified by, but not limited to, the following compounds:
2,2-dimethyl-6-hydroxychroman
2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman
2,2,5-trimethyl-8-tert-butyl-6-hydroxychroman
2,2,7,8-tetramethyl-6-hydroxychroman
2,2,5,7-tetramethyl-6-hydroxychroman
2,2,5,8-tetramethyl-6-hydroxychroman
2,2-dimethyl-7-tert-butyl-6-hydroxychroman
4-isopropyl-2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman
2,2,5,7,8-pentamethyl-6-hydroxychroman
4-isopropyl-2,2-dimethyl-7-tert-butyl-6-hydroxychroman
2,2-dimethyl-5-tert-butyl-6-hydroxychroman
2,5,7,8-tetramethyl-2-(4-methylpent-3-enyl)-6-hydroxychroman
2,5-dimethyl-8-tert-butyl-2-(4-methylpent-3-enyl)-6-hydroxychroman
2-methyl-2-(4-methylpent-3-enyl)-6-hydroxychroman,
2,2,5-trimethyl-6-hydroxychroman
2,2,7-trimethyl-6-hydroxychroman and
2,2,8-trimethyl-6-hydroxychroman.
The compound of the formula (1) is particularly preferably 2,2,5,7,8-pentamethyl-6-hydroxychroman.
In the present invention, component (a) may be one or more kinds of the compounds of the formula (1).
The substituents of the compound of the formula (2) or the formula (4), which is the constituent component of the stabilizer composition for organic polymer material of the present invention, are explained in the following.
In the formula (3) 
which is the substituent Q1 or Q2 in the formula (2) 
or the formula (4) 
R7 and R8 are the same or different and each is alkyl having 1 to 4 carbon atoms, wherein alkyl may be a straight or branched chain. Examples of the alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, with preference given to tert-butyl. It is particularly preferable that both of R7 and R8 be tert-butyl.
In the group of the above-mentioned formula (3), R9 is hydrogen atom or methyl, wherein, when R is methyl, R9 is particularly preferably substituted at the 5- or 6-position, most preferably at the 5-position, on the phenyl ring of the formula (3).
Particularly preferable examples of the group of the formula (3) include 2,4-di-tert-butylphenoxy and 2,4-di-tert-butyl-5-methylphenoxy.
In the formula (2) and formula (4), n1 is an integer of 1-10, preferably 1 or 2, particularly preferably 1. In the formula (2) and formula (4), i and j are 0 or 1, preferably 0.
When the component (b) is (b-1), the compound of the formula (2) is preferably the main component, wherein the compound of the formula (4) may not be contained.
Examples of the compound of the formula (2) or the formula (4), which is the constituent component of the stabilizer composition for organic polymer material of the present invention, include the following.
4,4xe2x80x2-Biphenylenediphosphonite compounds represented by tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite disclosed in JP-B-50-35096,
a composition containing tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite and corresponding biphenylenemonophosphonite disclosed in JP-A-1-254744,
a composition containing tetrakis(2,4-di-tert-butyl-6-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite and the like disclosed in JP-A-2-270892,
a composition containing tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonate and the like disclosed in JP-A-5-202078,
tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite compound disclosed in JP-A-5-178870,
and compounds disclosed in JP-A-8-231568 such as 2,4-di-tert-butylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl]phosphinite (or also called (2,4-di-tert-butylphenoxy)bis[4xe2x80x2-[bis(2,4-di-tert-butylphenoxy)phosphino]biphenyl-4-yl]phosphine),
2,4-di-tert-butylphenyl [4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl][4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butylphenyl bis[4xe2x80x2-bis(2,4-di-tert-5 butylphenoxy)phosphanylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butylphenyl [4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl][4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butyl-5-methylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl]phosphinite (or also called
(2,4-di-tert-butyl-5-methylphenoxy)bis[4xe2x80x2[bis(2,4-di-tert-butyl-5-methylphenoxy)phosphino]biphenyl-4-yl]phosphine),
2,4-di-tert-butyl-5-methylphenyl [4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl][4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphorylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butyl-5-methylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butyl-5-methylphenyl [4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl][4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphorylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butyl-5-methylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphorylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butyl-5-methylphenyl bis[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphorylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butyl-5-methylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butyl-5-methylphenoxy)phosphanylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butyl-6-methylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butyl-6-methylphenoxy)phosphanylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinite,
2,4-di-tert-butylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphanylbiphenyl-4-yl]phosphinate,
2,4-di-tert-butylphenyl(biphenyl-4-yl)[4xe2x80x2-bis(2,4-di-tert-butylphenoxy)phosphorylbiphenyl-4-yl]phosphinate and the like.
The compound of the formula (2) is particularly preferably tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite, or tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite. A composition containing tetrakis(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylenediphosphonite as the main component (50-85 wt %), and also (2,4-di-tert-butylphenoxy)bis[4xe2x80x2-[bis(2,4-di-tert-butylphenoxy)phosphino]biphenyl-4-yl]phosphine (5-15 wt %), [(2,4-di-tert-butylphenoxy)phosphino]biphenyl (5-20 wt %), tris(2,4-di-tert-butylphenyl)phosphite and the like (5-15 wt %), or a composition containing tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4xe2x80x2-biphenylenediphosphonite as the main component (50-85 wt %), and also (2,4-di-tert-butyl-5-methylphenoxy)bis[4xe2x80x2-[bis(2,4-di-tert-butyl-5-methylphenoxy)phosphino]biphenyl-4-yl]phosphine (5-15 wt %), [(2,4-di-tert-butyl-5-methylphenoxy)phosphino]biphenyl (5-20 wt %), tris(2,4-di-tert-butyl-5-methylphenyl)phosphite (5-15 wt %) and the like are most preferable.
The substituents of the compound of the formula (5) or of the formula (7), which is the constituent component of the stabilizer composition for organic polymer material of the present invention, are explained in the following.
The alkyl having 1 to 18 carbon atoms at R10 of the formula (5) and the formula (7), and at R11 of the formula (5) may be a straight or branched chain, and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like, with preference given to octadecyl.
The phenyl substituted by alkyl having 1 to 9 carbon atoms at R10 of the formula (5) and the formula (7) and at R11 of the formula (5) is, for example, methylphenyl, ethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl and the like.
The phenylalkyl having 7 to 9 carbon atoms at R11 of the formula (5) may have an alkyl moiety which may be a straight or branched chain. Examples thereof include benzyl, phenethyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl and the like.
R12 and R13 of a group of the formula (6) are the same or different and each is alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl, with preference given to tert-butyl. It is particularly preferable that R12 and R13 be both tert-butyl.
R14 of a group of the formula (6) is hydrogen atom or methyl. When R14 is methyl, R14 is preferably substituted at the 5- or 6-position on the phenyl ring.
Preferable examples of the group of the formula (6) include 2,4-di-tert-butylphenyl and 2,4-di-tert-butyl-6-methylphenyl.
Preferable examples of R10 of the formula (5) include dodecyl, octadecyl, phenyl, nonylphenyl, 2,4-di-tert-butylphenyl and 2,4-di-tert-butyl-6-methylphenyl.
Preferable examples of R11 of the formula (5) include methyl, ethyl, dodecyl, octadecyl, phenyl, nonylphenyl, 2,4-di-tert-butylphenyl and 2,4-di-tert-butyl-6-methylphenyl.
Preferable examples of R10 of the formula (7) include dodecyl, octadecyl, phenyl, nonylphenyl, 2,4-di-tert-butylphenyl and 2,4-di-tert-butyl-6-methylphenyl.
Specific examples of the compound of the formula (5) or of the formula (7) are
tris(2,4-di-tert-butylphenyl) phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,
triphenyl phosphite,
diphenyl alkyl phosphite,
phenyl dialkyl phosphite,
tris(nonylphenyl) phosphite,
trilauryl phosphite,
trioctadecyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and the like.
The substituents of the compound of the formula (8) or of the formula (9), which is the constituent component of the stabilizer composition for organic polymer material of the present invention, are explained in the following.
The definition of A in the formula (8) is first explained in the following. When q is 1, A is a group of the formula (10) 
wherein
R18 and R19 may be the same or different and each is alkyl having 1 to 4 carbon atoms, and R20 is hydrogen atom or alkyl having 1 to 4 carbon atoms, and when q is 2, A is alkylene having 2 to 18 carbon atoms, p-phenylene or p-biphenylene.
R18 and R19 of the group of the formula (10) are the same or different and each is alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, with preference given to methyl and tert-butyl.
R20 of the group of the formula (10) is hydrogen atom or alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl. R20 is preferably hydrogen atom or tert-butyl.
When R20 is alkyl having 1 to 4 carbon atoms, R20 is particularly preferably substituted at the 5- or 6-position, most preferably at the 6-position, on the phenyl ring.
Preferable examples of the group of the formula (10) include 2,4,6-tri-tert-butylphenyl, 2,4-di-tert-butylphenyl and 2,6-di-tert-butyl-4-methylphenyl.
The alkylene having 2 to 18 carbon atoms at A of the formula (8) may be a straight or branched chain, and may be, for example, ethylene, ethylidene, trimethylene, isopropylidene, tetramethylene, pentamethylene, hexamethylene and the like.
When q is 1, preferable examples of A include 2,4,6-tri-tert-butylphenyl, 2,4-di-tert-butylphenyl and 2,6-di-tert-butyl-4-methylphenyl.
In the formula (8), q is preferably 1.
R15 and R16 of the formula (8) are the same or different and each is alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl.
The definition of R17 in the formula (9) is explained in the following. R17 is independently alkyl having 1 to 18 carbon atoms, phenylalkyl having 7 to 9 carbon atoms, cyclohexyl, phenyl, or a group of the formula (11) 
wherein R21 and R22 are the same or different and each is alkyl having 1 to 4 carbon atoms or phenylalkyl having 7 to 9 carbon atoms, and R23 is hydrogen atom or alkyl having 1 to 4 carbon atoms.
The alkyl having 1 to 18 carbon atoms at R17 of the formula (9) may be a straight or branched chain, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like, with preference given to octadecyl.
The phenylalkyl having 7 to 9 carbon atoms at R17 of the formula (9) may have an alkyl moiety which may be a straight or branched chain.
Examples thereof include benzyl, phenethyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl and the like.
The alkyl having 1 to 4 carbon atoms at R21 and R22 of the formula (11) may be a straight or branched chain, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl, with preference given to methyl and tert-butyl.
The phenylalkyl having 7 to 9 carbon atoms at R21 and R22 of the formula (11) may have an alkyl moiety which may be a straight or branched chain. Examples thereof include benzyl, phenethyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl and the like.
R23 of the group of the formula (11) is hydrogen atom or alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl. Preferable examples of R23 include hydrogen atom and tert-butyl. When R23 is alkyl having 1 to 4 carbon atoms, R23 is particularly preferably substituted at the 5- or 6-position, most preferably at the 6-position, on the phenyl ring.
Preferable examples of R17 include 2,4-di-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,4-di(1-phenyl-1,1-dimethylmethyl)phenyl, 2,4,6-tri-tert-butylphenyl, octadecyl and isodecyl.
Specific examples of the compound of the formula (8) or of the formula (9) are
bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite,
bis(2,4-di(1-phenyl-1,1-dimethylmethyl)phenyl) pentaerythritol diphosphite,
(2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediol phosphite,
bisisodecyl pentaerythritol diphosphite,
bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite and the like.
The substituents of the compound of the formula (12), which is the constituent component of the stabilizer composition for organic polymer material of the present invention, are explained in the following.
In the formula (12), each R24 is the same or different and is alkyl having 1 to 5 carbon atoms. This alkyl may be a straight or branched chain and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl and the like. As R24, tert-butyl is preferable.
In the formula (12), each R25 is the same or different and is hydrogen atom or alkyl having 1 to 5 carbon atoms. This alkyl may be a straight or branched chain and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. As R25, tert-butyl is preferable.
Each R26 in the formula (12) is the same or different and is hydrogen atom or methyl, preferably hydrogen atom.
In the formula (12), R29 is alkyl having 1 to 4 carbon atoms. This alkyl may be a straight or branched chain and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl. As R29 methyl is preferable.
Preferable examples of R27 in the formula (12) include direct bond, methylene and ethylidene.
The alkyl having 1 to 18 carbon atoms at R28 of the formula (12) may be a straight or branched chain and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutan-1-yl, 2-methylbutan-2-yl, 2-methylbutan-3-yl, 2-methylbutan-4-yl, neopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.
The halogen atom at R28 of the formula (12) is exemplified by chlorine atom, bromine atom, fluorine atom and iodine atom, preferably fluorine atom.
The alkoxy having 1 to 8 carbon atoms at R28 of the formula (12) may be a straight or branched chain and is exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butyloxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like, with preference given to 2-ethylhexyloxy.
When n3 of the formula (12) is 1, preferable examples of R28 include fluorine atom and 2-ethylhexyloxy.
The compound of the formula (12) is specifically exemplified by
2,2-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite (also called 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin),
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,
2,2xe2x80x2, 2xe2x80x3-nitrilo[triethyltris(3,3xe2x80x2, 5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite] and the like.
The substituents of the compound of the formula (17), which is the constituent component of the stabilizer composition of the present invention for organic polymer material, are explained in the following.
R33 and R34 are the same or different and each is hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms, aralkyl having 7 to 12 carbon atoms or phenyl. The alkyl having 1 to 8 carbon atoms may be linear or branched and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, 6-methylheptyl, 1,1-dimethylhexyl, 2-ethylhexyl and the like. The cycloalkyl having 5 to 8 carbon atoms may be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. The cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms may be substituted by 2 or more alkyl, preferably substituted by 1 to 3 alkyl. The alkyl having 1 to 4 carbon atoms, which is a substituent on cycloalkyl, may be linear or branched and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like. The cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms may be 2-methylcyclopentyl, 2-methylcyclohexyl, 2-methyl-4-isopropylcyclohexyl and the like. The aralkyl having 7 to 12 carbon atoms contains a linear or branched alkyl having 1 to 6 carbon atoms, and is exemplified by benzyl, phenethyl, 3-phenylpropyl, xcex1-methylbenzyl, xcex1,xcex1-dimethylbenzyl and the like.
R33 is preferably tert-butyl, tert-pentyl, 1,1-dimethylhexyl, cyclohexyl or 2-methylcyclohexyl.
R34 is preferably methyl, tert-butyl or tert-pentyl.
Each R35 is the same or different and is hydrogen atom or alkyl having 1 to 8 carbon atoms. The alkyl having 1 to 8 carbon atoms may be linear or branched and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, 6-methylheptyl, 1,1-dimethylhexyl, 2-ethylhexyl and the like.
R35 is preferably hydrogen atom or methyl.
R33, R34 and R35 may be the same or different.
R36 is a direct bond, methylene, xe2x80x94CH (R42)xe2x80x94 where R42is alkyl having 1 to 7 carbon atoms or cycloalkyl having 5 to 8 carbon atoms, or sulfur atom. The alkyl having 1 to 7 carbon atoms at R42 may be linear or branched, and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl and the like. The cycloalkyl having 5 to 8 carbon atoms at R42 is exemplified by cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
R36 may be preferably a direct bond, methylene or xe2x80x94CH(R42)xe2x80x94 wherein R42 is methyl, ethyl, propyl, isopropyl, butyl, isobutylortert-butyl.
R37 is alkylene having 2 to 8 carbon atoms, *xe2x80x94R43xe2x80x94Oxe2x80x94COxe2x80x94R44xe2x80x94 or *xe2x80x94COxe2x80x94R44xe2x80x94 wherein R43 is alkylene having 1 to 8 carbon atoms, R44 is a direct bond or alkylene having 1 to 8 carbon atoms, and * means a bond on the oxygen atom side. The alkylene having 2 to 8 carbon atoms may be linear or branched, and is exemplified by ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-trimethylene and the like, with preference given to trimethylene. The alkylene having 1 to 8 carbon atoms at R43 or R44 may be linear or branched and is exemplified by methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, 2,2-dimethyl-1,3-trimethylene and the like. As R43, ethylene is preferable. As R44, a direct bond or ethylene is preferable.
R37 is preferably alkylene having 2 to 8 carbon atoms or *xe2x80x94R43xe2x80x94Oxe2x80x94COxe2x80x94R44xe2x80x94, more preferably ethylene, trimethylene, 2,2-dimethyl-1,3-trimethylene or *xe2x80x94CH2CH2xe2x80x94Oxe2x80x94COxe2x80x94CH2CH2xe2x80x94.
R38 and R40 are the same or different and each is hydrogen atom, alkyl having 1 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, cycloalkyl having 5 to 8 carbon atoms substituted by alkyl having 1 to 4 carbon atoms, aralkyl having 7 to 12 carbon atoms or phenyl. Examples of R38 and R40 are those recited above for R33 and R34.
R38 and R40 are preferably hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl and tert-pentyl.
One of R39 and R41 is hydroxyl group, alkoxy having 1 to 8 carbon atoms or aralkyloxy having 7 to 12 carbon atoms, and the other is hydrogen atom or alkyl having 1 to 8 carbon atoms. The alkoxy having 1 to 8 carbon atoms may be linear or branched and is exemplified by methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutyloxy, sec-butoxy, tert-butoxy and the like. The aralkyloxy having 7 to 12 carbon atoms contains linear or branched alkyl having 1 to 6 carbon atoms and is exemplified by benzyloxy, phenethyloxy, 3-phenylpropyloxy, xcex1-methylbenzyloxy, xcex1,xcex1-dimethylbenzyloxy and the like. The alkyl having 1 to 8 carbon atoms may be linear or branched and is exemplified by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, 3-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, 6-methylheptyl, 1,1-dimethylhexyl, 2-ethylhexyl and the like.
Preferably, one of R39 and R41 is hydroxyl group and the other is hydrogen atom or alkyl having 1 to 8 carbon atoms. More preferably, R39 is hydroxyl group, and R41 is hydrogen atom.
Examples of the compound of the formula (17) are as follows.
2,10-dimethyl-4,8-di-tert-butyl-6-{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethoxy}-12H-dibenzo[d,g][1,3,2]dioxaphosphocin,
6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetratert-butyldibenzo[d,f][1,3,2]dioxaphosphepin,
2,10-dimethyl-4,8-di-tert-butyl-6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]dibenzo[d,f][1,3,2]dioxaphosphepin and the like.
According to the present invention, one or more of these phosphorus antioxidants can be used in combination.
The phenolic antioxidant which is one of the constituent components of the stabilizer composition for organic polymer materials of the present invention is exemplified by a compound having one or more structures shown by the following formula (16) 
wherein R30 is alkyl having 1 to 5 carbon atoms, R31 is alkyl having 1 to 4 carbon atoms, R32 is hydrogen atom or methyl, and L is 
in a molecule and the like.
Specific examples of the phenolic antioxidant include, but not limited to,
n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,1,3-tris[2-methyl-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-5-tert-butylphenyl]butane,
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
2,6-di-tert-butyl-4-methylphenol,
2,4-dimethyl-6-tert-butylphenol,
2,6-di-tert-butyl-4-hydroxymethylphenol,
2,6-di-tert-butyl-4-ethylphenol,
2,4,6-tri-tert-butylphenol,
butylated hydroxyanisole,
isooctyl 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate,
distearyl (4-hydroxy-3-methyl-5-tert-butyl)benzylmalonate,
2,2xe2x80x2-methylenebis(4-methyl-6-tert-butylphenol),
2,2xe2x80x2-methylenebis(4-ethyl-6-tert-butylphenol),
4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol),
2,2xe2x80x2-butylidenebis(4-ethyl-6-tert-butylphenol),
4,4xe2x80x2-butylidenebis(3-methyl-6-tert-butylphenol),
2,2xe2x80x2-thiobis(4-methyl-6-tert-butylphenol),
4,4xe2x80x2-thiobis(3-methyl-6-tert-butylphenol),
styrenated phenol,
N,Nxe2x80x2-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocynnamide),
bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium,
1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol),
2,2xe2x80x2-methylenebis[6-(1-methylcyclohexyl)-4-methylphenol],
triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate],
ethylene glycol-bis(3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate),
2-tert-butyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenyl acrylate,
2,2xe2x80x2-oxamido-bis[ethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-dioctylthio-1,3,5-triazine,
bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl] terephthalate,
3,9-bis[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
1,3,5-tris[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanate,
2,2-thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate],
2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
2,4-di-octylthiomethyl-6-methylphenol and the like, as well as respective compounds of propyl gallate, octyl gallate or dodecyl gallate.
Preferable phenolic antioxidant is exemplified by
n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,1,3-tris[2-methyl-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-5-tert-butylphenyl]butane,
2,4-di-octylthiomethyl-6-methylphenol
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate,
3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane and the like.
Particularly preferable phenolic antioxidant is exemplified by, but not limited to,
n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxymethyl]methane,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like.
According to the present invention, one or more of these phenolic antioxidants can be used in combination.
The organic polymer to be stabilized by the inventive stabilizer composition is exemplified by synthetic organic polymer and natural organic polymer.
The synthetic organic polymer is exemplified by synthetic resin such as thermoplastic resin, thermosetting resin and the like.
The thermoplastic resin is exemplified by olefin resin, halogen-containing polymer, styrene resin, acrylic resin, thermoplastic polyester resin, polyamide resin, aromatic polycarbonate resin, polyacetal resin, polyethylene oxide resin, polyphenylene ether resin, polysulfone resin, polyurethane resin, petroleum resin, polyvinyl acetate resin, vinyl acetal resin, cellulose resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ketone resin, polyether imide resin, polyoxybenzoyl resin, polyimide resin, polymaleimide resin, polyamide-imide resin, polyarylate resin, fluororesin, ionomer, thermoplastic elastomer and the like, and mixtures thereof.
The aforementioned olefin resin is exemplified by homopolymer of xcex1-olefin having 2 to 8 carbon atoms (e.g., low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polypropylene, polybutene-1, polypentene, poly-3-methylbutylene and the like); xcex1-olefin copolymer (e.g., ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-butene-1 random copolymer, propylene-ethylene-butene-1 random copolymer and the like); copolymer of xcex1-olefin and other monomer (e.g., maleic anhydride modified polypropylene, ethylene-vinyl acetate copolymer and the like), and the like. Two or more kinds thereof or a mixture of these and other compatible polymer may be used.
These olefin resins may be one obtained by removing a catalyst residue after polymerization and thus somewhat purified, one obtained by relatively high purification, olefin resin containing a catalyst residue, which is obtained by using a highly active catalyst but without a catalyst removal step or with a simplified catalyst removal step, or particularly crystalline olefin resin obtained by using a Ziegler catalyst using a halogen-containing magnesium compound as a catalyst carrier or a chromium catalyst and without a catalyst residue removal step (see JP-B-62-4418 and 3-56245, U.S. Pat. No. 4,115,639). In addition, it may be an olefin resin having a very narrow molecular weight distribution, which is obtained using a metallocene single site catalyst (Journal of Polymer Science. Polymer Chemistry Edition, Vol. 23, p. 2151 (1985)).
The above-mentioned halogen-containing polymer is, for example, polyvinyl chloride, poylvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride-acrylic acid alkyl ester copolymer, chlorinated polyethylene and the like.
The above-mentioned styrene resin is, for example, polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, styrene-MMA copolymer, ABS resin, AES resin, ACS resin, AAS resin, EES resin and the like, and mixtures thereof and the like.
The above-mentioned acrylic resin is, for example, polyacrylate, polymethacrylate and the like.
The above-mentioned thermoplastic polyester resin is, for example, polyethylene terephthalate, polybutylene terephthalate and the like.
The above-mentioned polyamide resin is, for example, nylon 4, nylon 6, nylon 4/6, nylon 6/6, nylon 6/10, nylon 7, nylon 8, nylon 12, nylon 6/12, nylon 11/12, aramid and the like, mixtures of these and the like.
The thermosetting resin is, for example, unsaturated polyester resin, phenol resin, urea resin, melamine resin, epoxy resin, polyimide resin, silicone resin, diallyl phthalate resin, polyurethane resin, furan resin and the like.
In addition, the natural organic polymer is, for example, a natural rubber, a protein, a derivative of a cellulose and the like, mineral oil, animal or vegetable oil, wax, fats and oils and the like.
The organic polymer to be used for the inventive organic polymer material composition is particularly polyolefin resin, more particularly an xcex1-olefin homopolymer or an xcex1-olefin copolymer. When a stabilizer composition of the present invention is added to such organic polymer, a superior antioxidant effect can be achieved. The most preferable polyolefin resin is polyethylene or polypropylene.
The 6-hydroxychroman compound of the formula (1) 
wherein R1 is alkyl having 1 to 5 carbon atoms or alkenyl having 2 to 5 carbon atoms, R2 is alkyl having 1 to 5 carbon atoms, R3, R4 and R5 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms, and R6 is hydrogen atom or alkyl having 1 to 5 carbon atoms, to be used in the present invention can be synthesized according to the method described in JP-B-45-23146.
In the present invention, a compound of the formula 
wherein R1 is alkyl having 1 to 6 carbon atoms or alkenyl having 2 to 6 carbon atoms, R2 is methyl, R3, R4, R5 and R6 are the same or different and each is hydrogen atom or alkyl having 1 to 4 carbon atoms, can be used as a 6-hydroxychroman compound.
The above-mentioned phosphorus antioxidant and phenolic antioxidant are known compounds, most of which are commercially available as antioxidants and can be obtained easily. The phosphorus antioxidant of the formula (17) can be synthesized according to the method described in JP-A-11-222493.
The proportions of the 6-hydroxychroman compound (component (a)) of the formula (1) and phenolic antioxidants (component (b)) and phosphorus antioxidants (component (c)), relative to the total amount of the components (a), (b) and (c), is 0.5 wt %-10 wt % of component (a), 99.5 wt %-90 wt % of the total amount of component (b) and component (c), preferably 1.0 wt %-10 wt % of component (a), 99.0 wt %-90 wt % of the total amount of component (b) and component (c), more preferably 1 wt %-8 wt % of component (a), 99 wt %-92 wt % of the total amount of component (b) and component (c), more preferably 1 wt %-6.5 wt % of component (a), 99 wt %-93.5 wt % of the total amount of component (b) and component (c), particularly preferably 1.0 wt %-5.5 wt % of component (a), 99.0 wt %-94.5 wt % of the total amount of component (b) and component (c), and most preferably 1.0 wt %-4.5 wt % of component (a), 99.0 wt %-95.5 wt % of the total amount of component (b) and component (c), from the economical aspect.
Alternatively, the component (a) may be contained in a proportion of 1 wt %-20 wt %, and the total amount of the component (b) and the component (c) may be 99 wt %-80 wt %, relative to the total amount of the component (a), the component (b) and the component (c).
By using the inventive stabilizer composition for organic polymer material containing the 6-hydroxychroman compound of the formula (1) in a small amount in the above-mentioned range, an organic polymer material hardly colored and is superior in stability during processing can be obtained.
In the present invention, the weight ratio of component (b):component (c) is 9:1-1:9, preferably 4:1-1:4, more preferably 1:0.3-1:3, still more preferably 1:0.5-1:2.
By using the inventive stabilizer composition for organic polymer material having the weight ratio of the component (b) and the component (c) within the above-mentioned range, an organic polymer material superior in coloring prevention and stability during processing can be obtained.
The inventive stabilizer composition for organic polymer material has a content of the 6-hydroxychroman compound of the formula (1) of 0.0005 part by weight-0.025 part by weight, preferably 0.0005 part by weight-0.0100 part by weight, more preferably 0.001 part by weight-0.007 part by weight, still more preferably 0.001 part by weight-0.0055 part by weight, relative to 100 parts by weight of the organic polymer material composition. The content is generally 0.001 part by weight-0.005 part by weight, and from the economic aspect, preferably 0.001 part by weight-0.0045 part by weight.
The total amount of the 6-hydroxychroman compound of the formula (1), a phosphorus antioxidant and a phenolic antioxidant relative to 100 parts by weight of the organic polymer material composition is 0.01 part by weight-1 part by weight, preferably 0.02 part by weight -0.2 part by weight. By setting the amount to 0.01 part by weight -1 part by weight, an organic polymer material superior in coloring preventive function and that shows superior stability during processing can be obtained.
By further adding a sulfur antioxidant to the stabilized organic polymer material composition of the present invention, an organic polymer material having more superior stability can be obtained.
The sulfur antioxidant is not particularly limited but preferred are
dilauryl thiodipropionate,
lauryl stearyl thiodipropionate,
dimyristyl thiodipropionate,
distearyl thiodipropionate,
ditridecyl thiodipropionate,
tetrakis[(3-laurylthiopropionyloxy)methyl]methane,
tetrakis[(3-stearylthiopropionyloxy)methyl]methane,
bis[2-methyl-4-(3-n-alkyl(C12-C14)thiopropionyloxy)-5-tert-butylphenyl]sulfide and the like.
The organic polymer material composition of the present invention can contain one or more sulfur antioxidants. The sulfur antioxidant can be added to an organic polymer material composition in an amount of preferably 0.005 part by weight-5 parts by weight, more preferably 0.01 part by weight-1 part by weight, per 100 parts by weight of the organic polymer material composition. When two or more kinds of the sulfur antioxidants are used, the total amount preferably falls within the above-mentioned range.
By further adding an ultraviolet absorber and a light stabilizer to the stabilized organic polymer material composition of the present invention, a more stabilized organic polymer material can be obtained.
Examples of the ultraviolet absorber and light stabilizer include salicylic acid compound, benzophenone compound, benzotriazole compound, benzoate compound, cyanoacrylate compound, nickel compound, piperidine compound and the like.
Examples of the salicylic acid compound that can be used as an ultraviolet absorber include, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate and the like.
Examples of the benzophenone compound that can be used as an ultraviolet absorber include compounds such as
2,4-dihydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2,2xe2x80x2-dihydroxy-4,4xe2x80x2-dimethoxybenzophenone,
2-hydroxy-4-n-octyloxybenzophenone,
2-hydroxy-4-isooctyloxybenzophenone,
2-hydroxy-4-dodecyloxybenzophenone,
2-hydroxy-4-octadecyloxybenzophenone,
2-hydroxy-4-methoxy-2xe2x80x2-carboxybenzophenone,
bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane,
2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate,
2,2xe2x80x2,4,4xe2x80x2-tetrahydroxybenzophenone,
2-hydroxy-4-benzoyloxybenzophenone and the like.
Examples of the benzotriazole compound that can be used as an ultraviolet absorber include compounds such as
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole,
2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlrolobenzotriazole,
2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole,
2-[2-hydroxy-5-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole,
2-[2-hydroxy-3,5-bis(xcex1,xcex1-dimethylbenzyl)phenyl]-2H-benzotriazole,
condensate of methyl 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol,
2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole,
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol],
2-(2-hydroxy-5-tert-octylphenyl)benzotriazole,
2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and the like.
Examples of the benzoate compound that can be used as a light stabilizer include compounds such as
n-hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and the like.
Examples of the cyanoacrylate compound that can be used as an ultraviolet absorber include compounds such as
ethyl 2-cyano-3,3-diphenylacrylate,
octyl 2-cyano-3,3-diphenylacrylate and the like.
Examples of the nickel compound that can be used as an ultraviolet absorber include compounds such as
2-ethylhexylamine nickel,
nickel dimethyldithiocarbamate,
[2,2xe2x80x2-thiobis[4-(1,1,3,3-tetramethylbutyl)phenolate]]-n-butylamine nickel,
[2,2-thiobis[4-(1,1,3,3-tetramethylbutyl)phenolate]] nickel and the like.
Examples of the piperidine compound that can be used as a light stabilizer include compounds such as
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
poly[[6-(1,1,3,3-tetramethylbutyl)imino-s-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]],
poly[(6-morpholino-s-triazine-2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]](cyanuric chloride/tert-octylamine/1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane condensate),
1-hydroxyethyl-2,2,6,6-tetramethyl-4-piperidinol/succinic acid condensate,
N,Nxe2x80x2-bis(3-aminopropyl)ethyldiamine/2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-6-chloro-1,3,5-triazine condensate and the like.
Examples of preferable compound that can be used as an ultraviolet absorber and light stabilizer include compounds such as
2-hydroxy-4-n-octyloxybenzophenone,
2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole,
2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole,
bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate,
poly[[6-(1,1,3,3-tetramethylbutyl)imino-s-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]](cyanuric chloride/tert-octylamine/1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane condensate) and the like.
The organic polymer material composition of the present invention can contain one or more kinds of ultraviolet absorbers or light stabilizers. The ultraviolet absorber or light stabilizer can be added in an amount of preferably 0.005 part by weight-5 parts by weight, more preferably 0.01 part by weight-1 part by weight, per 100 parts by weight of organic polymer material composition. When two or more kinds of ultraviolet absorbers or light stabilizers are used, the total amount thereof is preferably within the above-mentioned range.
Where necessary, one or more kinds of other additives, that do not markedly impair the properties of the stabilized organic polymer material composition of the present invention, can be used concurrently, such as hydrotalcites, metal soap (e.g., calcium stearate), heavy metal inactivating agent (e.g., hydrazine compound), organic tin stabilizer [e.g., monoalkyltin tris(octyl thioglycolate), dialkyltin bis(octyl thioglycolate), monoalkyltin tris(monoalkyl maleate) and dialkyltin bis(monoalkyl maleate)], epoxy compound (e.g., epoxidized soybean oil and epoxyoctyl stearate), various organic pigments, flame retardant (e.g., phosphate), antistatic agent (e.g., cationic or anionic surfactant), lubricant (e.g., fatty acid amide and lower alcohol esters of fatty acid), acrylic polymer processing aid, plasticizer (e.g., di-2-ethylhexyl phthalate and di-2-ethylhexyl adipate), filler (e.g., aluminum oxide), blowing agent (e.g., sodium bicarbonate and azodicarbonamide) and the like.
The stabilized organic polymer material composition of the present invention can, where necessary, contain crystalline nucleating agent, clarifying agent and the like.
Examples of the crystalline nucleating agent and clarifying agent include,
bis(p-tert-butyl benzoate)hydroxyalminum,
sodium bis(4-tert-butylphenyl)phosphate,
sodium 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenyl)phosphate, dibenzylidenesorbitol,
2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenyl)phosphate hydroxyaluminum,
a composition containing 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenyl)phosphate hydroxyaluminum and lithium stearate (1:1),
bis(p-methylbenzylidene)sorbitol,
bis(p-ethylbenzylidene)sorbitol,
bis(p-chlorobenzylidene)sorbitol and the like.
The organic polymer material composition of the present invention can be prepared by mixing a 6-hydroxychroman compound, a phenolic antioxidant, a phosphorus antioxidant, and where necessary, a sulfuric antioxidant, an ultraviolet absorber, a light stabilizer or other additive, upon weighing predetermined amounts thereof, with an organic polymer. Alternatively, a 6-hydroxychroman compound, a phenolic antioxidant, a phosphorus antioxidant, and where necessary, a sulfuric antioxidant, an ultraviolet absorber, a light stabilizer or other additive are mixed upon weighing predetermined amounts thereof, to give the stabilizer composition of the present invention. The obtained stabilizer composition is mixed with an organic polymer to give the organic polymer material composition of the present invention. The organic polymer material composition may be kneaded after mixing or may be subjected to extrusion and the like.
For mixing, a mixer conventionally used for mixing additives with an organic polymer, such as a ball mill, a pebble mill, a tumbling mixer, a change-can mixer, a supermixer (Henschel mixer) and the like can be used. For admixing, a kneader conventionally used for kneading additives with an organic polymer, such as a mixing roll, a Banbury mixer, a xcexa3 blade mixer, a high-speed biaxial continuous mixer, an extruder type kneader and the like can be used.
The organic polymer material composition thus obtained can be formed into a desired product by various molding methods conventionally known for organic polymer material, such as an injection molding method, an extrusion molding method, a calendar molding method, a blow molding method, a compression molding method and the like. The product is free of particular limitation, and may be used outdoor or indoor, which use is specifically exemplified by parts of electric appliances, parts of electronic products, parts of agricultural machinery, products for agricultural use, parts of fishery machines, products for fishery use, parts of automobile vehicles, daily needs, sundries and the like.